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EP0467363B1 - Verfahren zur katalytischen Reinigung von Abgasen - Google Patents

Verfahren zur katalytischen Reinigung von Abgasen Download PDF

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Publication number
EP0467363B1
EP0467363B1 EP91112030A EP91112030A EP0467363B1 EP 0467363 B1 EP0467363 B1 EP 0467363B1 EP 91112030 A EP91112030 A EP 91112030A EP 91112030 A EP91112030 A EP 91112030A EP 0467363 B1 EP0467363 B1 EP 0467363B1
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EP
European Patent Office
Prior art keywords
catalyst
earth metal
nickel
zeolite
rare earth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91112030A
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English (en)
French (fr)
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EP0467363A1 (de
Inventor
Akinori Eshita
Senshi Kasahara
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Tosoh Corp
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Tosoh Corp
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Publication date
Priority claimed from JP2189342A external-priority patent/JP2969843B2/ja
Priority claimed from JP2409704A external-priority patent/JPH04210244A/ja
Priority claimed from JP2411788A external-priority patent/JPH04222635A/ja
Application filed by Tosoh Corp filed Critical Tosoh Corp
Publication of EP0467363A1 publication Critical patent/EP0467363A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a method of removing nitrogen oxides, carbon monoxide and hydrocarbons from an exhaust gas, comprising bringing an oxygen-rich combustion exhaust gas containing the aforementioned components into contact with a catalyst comprising (i) a zeolite having an SiO 2 /Al 2 O 3 molar ratio of at least 15, (ii) nickel and (iii) a rare earth metal or an alkaline earth metal, nickel and the rare earth metal or the alkaline earth metal being introduced in the zeolite by an ion-exchange method, with the proviso that the catalyst does neither comprise copper nor cobalt apart from unavoidable impurities.
  • a lean fuel combustion i.e., combustion at a relatively low fuel/oxygen ratio
  • combustion at a relatively low fuel/oxygen ratio has become necessary for recent gasoline engines, to obtain a low fuel consumption and reduce the quantity of the carbonic acid gas emitted, but since the exhaust gas of this lean combustion gasoline engine is oxygen-rich, the conventional ternary catalysts as described above cannot be employed, and thus a practical method of removing these detrimental components has not yet been discovered.
  • Japanese Unexamined Patent Publication (Kokai) No. 1-130735 proposes a catalyst which can selectively reduce the nitrogen oxides even in an oxygen-rich exhaust gas containing a trace amount of a reducing agent such as unburnt carbon monoxide and hydrocarbons.
  • EP-A-0 373 665 discloses a method for cleaning an exhaust gas by bringing the exhaust gas into contact with a crystalline aluminosilicate having a primary particle size of 0.5 ⁇ m or more and containing Group 1b and/or Group VIII metal ions.
  • EP-A-0 020 799 discloses a method for treating an exhaust gas using a catalyst comprising a hydrophobic zeolite Y having a Group VIII metal supported thereon.
  • EP-A-0 362 966 discloses a method of a denitrizing NO x using a catalyst comprising a zeolite, e.g. an X-type zeolite having usually an Si0 2 /Al 2 O 3 molar ratio of about 2 to 3, an alkali or alkaline earth metal and Ni.
  • a zeolite e.g. an X-type zeolite having usually an Si0 2 /Al 2 O 3 molar ratio of about 2 to 3, an alkali or alkaline earth metal and Ni.
  • EP-A-0 415 410 which represents prior art under Art. 54(3) EPC, discloses a catalyst for reducing nitrogen oxides from an exhaust gas containing the same in an oxygen rich atmosphere comprising (i) a zeolite having a molar ratio of Si0 2 /Al 2 O 3 of at least 10, (ii) copper, and (iii) a rare earth ion, an alkaline earth metal and/or a valence variable metal.
  • EP-A-0 491 360 which represent prior art under Art. 54(3) EPC, discloses a catalyst for purifying an exhaust gas to remove nitrogen oxides, carbon monoxide and hydrocarbons from an oxygen-rich exhaust gas containing nitrogen oxides, carbon monoxide and hydrocarbons comprising (i) a zeolite having an Si0 2 /Al 2 O 3 molar ratio of at least 15 and (ii) (a) cobalt, (b) a rare earth metal and (c) silver, or nickel and/or zinc, or platinum and/or manganese, or copper and/or rhodium, incorporated thereinto.
  • the above object is achieved by a method of removing nitrogen oxides, carbon monoxide and hydrocarbons from an exhaust gas, comprising bringing an oxygen-rich combustion exhaust gas containing the afore-mentioned components into contact with a catalyst comprising a zeolite having an SiO 2 /Al 2 O 3 molar ratio of at least 15, nickel and a rare earth metal or an alkaline earth metal, nickel and the rare earth metal or the alkaline earth metal being introduced in the zeolite by an ion-exchange method, with the proviso that said catalyst does neither contain copper nor cobalt apart from unavoidable impurities.
  • the zeolite described above generally has the composition expressed by the formula below: xM 2/n O ⁇ Al 2 O 3 ⁇ ySiO 2 ⁇ zH 2 O (where n is the valence of a cation M, x is a number of from 0.8 to 2, y is a number of at least 2, and z is a number of at least 0).
  • the zeolite usable in the present invention essentially must have an SiO 2 /Al 2 O 3 molar ratio of at least 15.
  • the upper limit of the SiO 2 /Al 2 O 3 molar ratio is not particularly limited, but when the SiO 2 /Al 2 O 3 molar ratio is less than 15, the zeolite per se has a low heat resistance and low durability, and thus the catalyst does not have a sufficient heat resistance and durability.
  • zeolites having an SiO 2 /Al 2 O 3 molar ratio of from about 15 to about 1,000 are employed.
  • a zeolite having a lower limit of the SiO 2 /Al 2 O 3 molar ratio of at least 15 is employed.
  • the zeolite usable for the catalyst used according to the present invention may be a natural zeolite or synthetic zeolite, and the method used for the production of these zeolites is not particularly limited.
  • zeolites such as mordenite, ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-20, etc., can be used, and these zeolites can be used as the catalyst used for the present invention either as it is or after conversion to an NH 4 type or an H type through an ion-exchange, by treating same with an ammonium salt, a mineral acid, or the like.
  • the zeolite usable in the present invention essentially must contain nickel.
  • the nickel content is not particularly limited, it is preferably from 0.5 to 1.7 molar times the Al 2 O 3 molar number in the zeolite.
  • the zeolite usable in the present invention must contain a rare earth metal or an alkaline earth metal besides nickel.
  • the nickel content, the content of the rare earth metal and the content of the alkaline earth metal are from 0.5 to 1.7 times, 0.1 to 0.8 times, and 0.1 to 1 time the alumina content, in terms of the molar ratio in the zeolite, respectively, and the sum of the contents of the nickel and the rare earth metal or the alkaline earth metal is from 1.0 to 2.5 times.
  • the nickel content is less than 0.5 times, the catalyst may be unsuitable for use as a catalyst, and when greater than 1.7 times, the durability and activity thereof proportional to such a nickel content cannot be easily obtained.
  • the content of the rare earth metal or the alkaline earth metal is less than the lower limit described above, an improved durability and catalytic activity might not be obtained, and when higher than the upper limit described above, an effect corresponding to the amount of addition cannot be easily obtained.
  • the methods of causing the zeolite to contain nickel, the rare earth metal and the alkaline earth metal are not particularly limited; an ion-exchange, impregnation and support can be used, but the ion-exchange is preferred.
  • any salts can be used as the salts for the ion-exchange of nickel, and examples of such salts include nitrates, chlorides, acetates and sulfates. Preferably divalent acetates are used.
  • the number of exchanges made by the ion-exchange is not particularly limited, as long as the exchange ratio is high. When the exchange ratio is low, the ion exchange may be repeated more than twice. The upper limit of the number of ion exchanges is not particularly limited, but is generally from two to five times.
  • the ion-exchange method may be a usual ion-exchange method, such as a method which charges a nickel salt into a slurry of the zeolite and the mixture or a method using stirring, to thereby charge the zeolite into an aqueous solution of the nickel salt.
  • the liquid temperature is from 20 to 100°C, preferably from 40 to 90°C
  • the concentration of the nickel salt in the aqueous solution is from 0.01 to 1 mol/l, preferably from 0.1 to 1 mol/l.
  • the nickel concentration is less than 0.01 mol/l, the operability will become poor because a large amount of an aqueous solution is necessary.
  • the solid-liquid ratio of the zeolite and the aqueous solution is not particularly limited, as long as it can be sufficiently stirred, and the solid content concentration of the slurry is preferably from 5 to 50%.
  • the ion-exchange time is not particularly limited, and may be at least five hours per time, preferably at least ten hours per time. When the time is shorter than the value described above, the ion-exchange ratio will drop to some extent.
  • the salts used for the ion-exchange of the rare earth metal may be those which are water-soluble, and preferably are nitrates and chlorides having a high solubility.
  • the kind of rare earth metal is not particularly limited, but preferably La, Ce, Y and Nd are used.
  • the liquid temperature is from 20 to 100°C, preferably from 40 to 90°C
  • the concentration of the rare earth metal salt in the aqueous solution is from 0.01 to 5 mol/l, preferably from 0.1 to 2 mol/l.
  • the solid-liquid ratio of the zeolite and the aqueous solution is not particularly limited, as long as it can be sufficiently stirred.
  • the solid content concentration of the slurry is preferably from 5 to 50%.
  • any salts can be used as the salts for the ion-exchange of the alkaline earth metal, but preferably nitrates or chlorides having a high solubility are used.
  • Be, Mg, Ca, Sr, Ba and Ra can be used as the alkaline earth metal, preferably Sr or Ba is used.
  • the ion-exchange of the alkaline earth metal may be carried out in the same way as that of the rare earth metal.
  • the sample is subjected to solid-liquid separation, washing and drying, and thereafter, is used as the catalyst. If necessary, it is used as the catalyst after baking.
  • the rare earth metal, the alkaline earth metal and nickel can be used after they are subjected by evaporation to dryness or the like.
  • a usual method can be employed for the evaporation to dryness.
  • a method which charges the zeolite into an aqueous solution containing the rare earth metal or nickel, and evaporates water as the solvent by a dryer or the like can be used.
  • concentrations of the rare earth metal or alkaline earth metal and nickel in the aqueous solution are not particularly limited, as long as the rare earth metal or alkali earth metal or nickel is uniformly deposited; the concentration of each is generally from 0.01 to 1 mol/l.
  • the sequence of containing the rare earth metal or the alkaline earth metal and nickel is not particularly limited, and when contained by the ion-exchange treatment, the sequence whereby first the rare earth metal or the alkaline earth metal is contained and then the nickel, is preferred.
  • the ion-exchange treatment may be carried out simultaneously in the co-presence of the nickel ions and the rare earth metal ions or the alkaline earth metal ions.
  • the silica/alumina molar ratio of the exhaust gas purifying catalyst is not substantially different from the silica/alumina molar ratio of the zeolite base used, and further, the crystal structure of the exhaust gas purifying catalyst does not substantially change before and after the ion-exchange treatment.
  • the catalyst used in the present invention can be used after mixing with a binder such as a clay mineral, and then molding.
  • the zeolite can be premolded and then nickel contained in the zeolite molded article by the ion-exchange treatment.
  • the binder used when molding this zeolite is a clay mineral such as kaolin, attapulgite, montmorillonite, bentonite, allophane, sepiolite, etc., and a metal oxide such as silica, alumina, silica-alumina, and so forth.
  • the raw zeolite may be a binderless zeolite molded article obtained by directly synthesizing a molded article without using the binder.
  • the zeolite may be obtained by wash-coating the zeolite on a honeycomb base made of cordierite or a metal.
  • the operation temperature of the catalyst in present invention may be in the range of 200 to 800°C and the gas hourly space velocity (GHSV) may be from 100 to 500,000 hr -1 .
  • GHSV gas hourly space velocity
  • oxygen-rich combustion exhaust gas to which the present invention is directed means an exhaust gas which contains oxygen in excess of the amount of oxygen necessary for completely oxidizing carbon monoxide, hydrocarbons and hydrogen contained in the exhaust gas, and examples of such an exhaust gas include the exhaust gas emitted from an internal combustion engine of an automobile, particularly under the state where an air-fuel ratio is high (i.e., a "lean range").
  • the performance of the exhaust gas purifying catalyst described above is not changed when applied to an exhaust gas which contains carbon monoxide, hydrocarbons and hydrogen, but is not oxygen-rich.
  • the ion-exchange treatment was carried out eight times in the same way as in Reference Example 1.
  • the product was used as the Reference Catalyst 2, and the nickel content was found to be 2.01 times, as divalent nickel, with respect to the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out only once, in the same way as in Reference Example 1, and the nickel content in this zeolite was found to be 0.68 times, as divalent nickel, with respect to the Al 2 O 3 molar number.
  • the resulting nickel-containing zeolite was used as the Reference Catalyst 6.
  • the evaporation to dryness was effected in the same way as in Example 4, except that the nickel content corresponded to 7% of the zeolite weight, when calculated as metal nickel.
  • the nickel content in this zeolite was found to be 2.98 times, as divalent nickel, with respect to the Al 2 O 3 molar number.
  • the resulting nickel-containing zeolite was used as the Reference Catalyst 6.
  • Comparative Example 1 Preparation of Comparative Catalyst 1
  • the mixture was stirred at 80°C for 16 hours, and after the slurry was subjected to solid-liquid separation, the resulting zeolite cake was charged again into the aqueous nickel solution having the same composition as described above, which was prepared again, and the same operations were carried out. After the solid-liquid separation, the product was washed with distilled water, dried at 100°C for 10 hours, and used as the Catalyst 1. When the lanthanum and nickel contents of this catalyst were examined by chemical analysis, it was found that the lanthanum content was 0.33 times, and the nickel content was 1.25 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 1, except that the rare earth metal used was cerium.
  • This catalyst was used as the Catalyst 2.
  • the cerium and nickel contents of this catalyst were examined by chemical analysis, it was found that the cerium content was 0.13 times and the nickel content was 1.18 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 1, except that the rare earth metal used was yttrium.
  • This catalyst was used as the Catalyst 3.
  • yttrium and nickel contents of this catalyst were examined by chemical analysis, it was found that yttrium content was 0.12 times and the nickel content was 1.08 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 1, except that the rare earth metal used was neodymium.
  • This catalyst was used as the Catalyst 4.
  • the neodymium and nickel contents of this catalyst were examined by chemical analysis, it was found that the neodymium content was 0.11 times and the nickel content was 1.04 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the product was washed with distilled water, subsequently charged into 180 g of an aqueous solution of lanthanum chloride having a concentration of 1.09 mol/l, and stirred at 80°C for 16 hours. After the solid-liquid separation, the product was washed with distilled water and dried at 110°C for 10 hours.
  • This catalyst was used as the Catalyst 5. When the lanthanum and nickel contents of this catalyst were examined by chemical analysis, it was found that the lanthanum content was 0.44 times and the nickel content was 1.18 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • this zeolite When the nickel content of this zeolite was examined by chemical analysis, it was found that the nickel content was 1.41 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite. Furthermore, 20 g of this zeolite was charged into 29 ml of a 0.05 mol/l aqueous lanthanum nitrate solution containing lanthanum, in an amount corresponding to 1 wt% as metal lanthanum, and was dried at 85°C for 10 hours, and subsequently at 110°C for 10 hours, for an evaporation to dryness. The resulting catalyst was used as the Catalyst 12.
  • the resulting zeolite cake was charged into the aqueous nickel solution having the composition described above, which was again prepared, and similar operations were carried out.
  • the product was washed with distilled water, dried at 110°C for 10 hours and was used as the Catalyst 7.
  • the barium and nickel contents of this catalyst were examined by chemical analysis, it was found that the barium content was 0.47 times and the nickel content was 1.25 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 7, except that the alkaline earth metal used was strontium.
  • the catalyst was used as the Catalyst 8. When the strontium and nickel contents of this catalyst were examined by chemical analysis, it was found that the strontium content was 0.25 times and the nickel content was 1.18 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 8, except that the alkaline earth metal used was magnesium.
  • the catalyst was used as the Catalyst 9. When the magnesium and nickel contents of this catalyst were examined by chemical analysis, it was found that the magnesium content was 0.16 times and the nickel content was 1.08 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the ion-exchange treatment was carried out in the same way as in Example 7 except that the alkaline earth metal used was calcium.
  • the catalyst was used as the Catalyst 16. When the calcium and nickel contents of this catalyst were examined by chemical analysis, it was found that the calcium content was 0.14 times and the nickel content was 1.04 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • the product was washed with distilled water, and subsequently, charged into 180 g of an aqueous solution of barium chloride having a concentration of 1.09 mole/l and stirred at 80°C for 16 hours.
  • the product was distilled washed with distilled water, dried at 110°C for 10 hours, and used as the Catalyst 11.
  • the barium and nickel contents of this catalyst were examined by chemical analysis, it was found that the barium content was 0.62 times and the nickel content was 1.18 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite.
  • this zeolite was examined by chemical analysis, it was found that the nickel content was 1.41 times, as divalent nickel, the Al 2 O 3 molar number of the zeolite. Furthermore, 20 g of this zeolite was charged into 29 ml of an aqueous solution of barium nitrate having a concentration of 0.05 mol/l and containing barium in the amount corresponding to 1 wt% as metal barium, and the product was dried at 85°C for 10 hours, and subsequently, at 110°C for 10 hours, for an evaporation to dryness. This catalyst was used as the Catalyst 12.
  • reaction gas A gas having the following composition (hereinafter referred to as the "reaction gas") was passed through the reactor at flow rate of 600 ml/min (30,000 hr -1 of GHSV (gas hourly space velocity)), and a pre-treatment was carried out by raising the temperature to 500°C and keeping the reactor at that temperature for 0.5 hours.
  • Table 1 shows the results of an evaluation of the durability of each catalyst, in terms of the change of the maximum purification efficiency in the Reactions 1 and 2, using NO, i.e., nitrogen oxides, as the detrimental components in the reaction gas.
  • the catalyst used in the present invention has a higher catalytic activity at the initial stage, and after held at 800°C for 5 hours in the reaction gas, and a higher exhaust gas purification capacity than the Comparative Catalysts, and exhibits a very high heat-resistance and durability. Accordingly, the present invention provides effects such that a purification of nitrogen oxides, carbon monoxide and hydrocarbons can be achieved by bringing the catalyst of the present invention into contact with the exhaust gas, even in an oxygen-rich state.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Claims (10)

  1. Verfahren zur Entfernung von Stickstoffoxiden, Kohlenmonoxid und Kohlenwasserstoffen aus einem Abgas, umfassend das In-Kontakt-Bringen eines sauerstoffreichen Verbrennungsabgases, das die vorstehend erwähnten Bestandteile enthält, mit einem Katalysator, der
    einen Zeolithen mit einem SiO2/Al2O3-Molverhältnis von mindestens 15,
    Nickel und
    ein Seltenerdmetall oder ein Erdalkalimetall umfaßt, wobei das Nickel und das Seltenerdmetall oder das Erdalkalimetall in den Zeolithen mittels eines Ionenaustauschverfahrens eingebracht werden, unter der Bedingung, daß der Katalysator abgesehen von unvermeidlichen Verunreinigungen weder Kupfer noch Kobalt enthält.
  2. Verfahren nach Anspruch 1, in dem die GHSV im Bereich von 100 bis 500.000 h-1 liegt.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, in dem die Betriebstemperatur des Katalysators im Bereich von 200 bis 800 °C liegt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, in dem das SiO2/Al2O3-Molverhältnis im Bereich von 15 bis 1000 liegt.
  5. Verfahren nach Anspruch 1, in dem der Nickelgehalt, ausgedrückt in Form des Molverhältnisses von Ni/Al2O3, 0,5 bis 1,7 beträgt.
  6. Verfahren nach Anspruch 1, in dem der Gehalt an Seltenerdmetall, ausgedrückt in Form des Molverhältnisses von Seltenerdmetall/Al2O3, 0,1 bis 0,8 beträgt.
  7. Verfahren nach Anspruch 1, in dem der Gesamtgehalt an Nickel und Seltenerdmetall oder Nickel und Erdalkalimetall, ausgedrückt in Form des Molverhältnisses von (Ni + Seltenerdmetall)/Al2O3 oder (Ni + Erdalkalimetall)/Al2O3, 1,0 bis 2,5 beträgt.
  8. Verfahren nach Anspruch 1, in dem das Seltenerdmetall mindestens ein Element ist, das aus der Gruppe bestehend aus La, Ce, Y und Nd ausgewählt ist.
  9. Verfahren nach Anspruch 1, in dem der Gehalt an Erdalkalimetall, ausgedrückt in Form des Molverhältnisses von Erdalkalimetall/Al2O3, 0,1 bis 1,0 beträgt.
  10. Verfahren nach Anspruch 1, in dem das Erdalkalimetall mindestens ein Element ist, das aus der Gruppe bestehend aus Be, Mg, Ca, Sr, Ba und Ra ausgewählt ist.
EP91112030A 1990-07-19 1991-07-18 Verfahren zur katalytischen Reinigung von Abgasen Expired - Lifetime EP0467363B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2189342A JP2969843B2 (ja) 1990-07-19 1990-07-19 排気ガス浄化触媒の使用方法
JP189342/90 1990-07-19
JP409704/90 1990-12-11
JP2409704A JPH04210244A (ja) 1990-12-11 1990-12-11 排ガス浄化触媒
JP411788/90 1990-12-20
JP2411788A JPH04222635A (ja) 1990-12-20 1990-12-20 排ガスの浄化触媒

Publications (2)

Publication Number Publication Date
EP0467363A1 EP0467363A1 (de) 1992-01-22
EP0467363B1 true EP0467363B1 (de) 1998-04-22

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EP91112030A Expired - Lifetime EP0467363B1 (de) 1990-07-19 1991-07-18 Verfahren zur katalytischen Reinigung von Abgasen

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US (1) US5514355A (de)
EP (1) EP0467363B1 (de)
AU (1) AU651601B2 (de)
CA (1) CA2046951A1 (de)
DE (1) DE69129283D1 (de)

Cited By (1)

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US6319484B1 (en) 1999-12-14 2001-11-20 Engelhard Corporation Compositions for abatement of volatile organic compounds and apparatus and methods using the same

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CN1047106C (zh) * 1993-12-11 1999-12-08 中国科学院大连化学物理研究所 催化裂化干气中乙烯与甲苯制对甲基乙苯用的沸石催化剂
US5834395A (en) * 1995-03-24 1998-11-10 Next Generation Catalyst Research Institute, Co., Ltd. Catalyst for controlling emissions
CN1046435C (zh) * 1995-06-15 1999-11-17 华南理工大学 甲烷选择性氧化制合成气的催化剂
DE19745548C2 (de) * 1997-10-10 1999-09-30 Mannesmann Ag Katalysator für die Alkylierung von Olefinen, Verfahren zur Herstellung des Katalysators und Verwendung des Katalysators zur Alkylierung
AUPP607198A0 (en) * 1998-09-21 1998-10-15 University Of Queensland, The Process and catalysts for the methanation of oxides of carbon
US7021049B2 (en) * 2000-09-29 2006-04-04 Ford Global Technologies, Llc Vehicle sulfur oxide trap and related method
EP1316359A1 (de) * 2001-12-03 2003-06-04 Rhodia Electronics and Catalysis Verfahren zur Reduktion von Stickoxidemissionen unter Verwendung von Ferrierit
AU2002361338A1 (en) * 2001-11-26 2003-06-10 Atofina Research Composition based on a ferrierite and its use in a gas treatment method for reducing nitrogen oxide emissions
US7094722B2 (en) * 2002-12-20 2006-08-22 Caterpillar Inc. NOx catalyst and method of suppressing sulfate formation in an exhaust purification system
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DE69129283D1 (de) 1998-05-28
AU8110591A (en) 1992-01-23
CA2046951A1 (en) 1992-01-20
EP0467363A1 (de) 1992-01-22
US5514355A (en) 1996-05-07
AU651601B2 (en) 1994-07-28

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